JPH0971752A - Composition for composite fire-resistant coating, and composite fire-resistant coating layer and forming method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composite fire-resistant coating layer excellent in long- term weatherability. SOLUTION: This compsn. contains a synthetic thermoplastic vinyl resin, a petroleum resin, a phosphorus flame retardant, a melamine compd., a triazine compd., an N-nitroso compd., an azo compd., at least one thermally decomposable blowing agent selected from among a sulfonhydrazide compd. and its derivs., a polyhydric alcohol as a char-forming agent, and a chlorine-contg. plasticizer. A composite fire-resistant coating layer is formed by forming a fire-resistant coating layer from the compsn. on an object to be coated and applying a topcoating material mainly comprising a silicone-modified acrylic resin or a fluorourethane resin on the above-formed fire-resistant coating layer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a composite fireproof coating composition, a composite fireproof coating layer, and a method for forming the same.

[0002]

2. Description of the Related Art Conventionally, in steel-framed buildings and civil engineering structures, a fire-resistant coating material is coated on the surface of the steel frame in order to prevent the strength of the steel frame from lowering in the event of a fire. Foaming type fire-resistant paint, which is one of such fire-resistant coating materials, is a thin coating film when there is no fire, but the components in the coating film react when the temperature rises during a fire, resulting in thick foam carbonization. Form a heat insulating layer. The foamed carbonized heat insulation layer delays the transfer of heat to the steel frame, and at the same time, the non-combustible gas generated when foaming exerts a fire extinguishing action.

Since such a fire-resistant paint has a thinner coating film than a non-foaming type thick film fire-resistant coating material, it may not be noticeable and may give a feeling of pressure even in a part that is invisible to the human eye. In addition, because of the construction of the fireproof coating layer, the coating amount can be reduced due to the thinness.

Further, such a refractory paint does not require a conventional high-discharging pressure-feeding device for constructing a thick film refractory coating material,
Since it can be used with ordinary coating equipment for paints, it is also considered promising as a material with excellent workability, and it is a material that is rapidly becoming widespread at present depending on the construction site.

By the way, the foaming type fire-resistant coating material is required to always exhibit excellent fire-resisting performance in preparation for a fire that cannot be predicted when it will occur. For that purpose, the coating film will not deteriorate and deteriorate as much as possible. It is necessary to maintain constant quality over a long period of time. Therefore, the coating film is required to have excellent weather resistance, particularly when it is used in a portion exposed to the outside air.

However, these conventional refractory paints are
Flame retardants, foaming agents, etc. are included as essential components, but since these are easily dissolved in water, when the fire-resistant coating film is used in areas with high dew condensation even outdoors or indoors where it is exposed to rain. However, there is a risk that these components will dissolve and the coating film will deteriorate. Therefore, when a fire actually occurs, the reaction of each component that should originally form the foamed carbonized heat insulating layer is insufficient or does not occur at all, and the fire insulating properties may not be sufficiently exhibited.

[0007] In addition, in parts exposed to sunlight both indoors and outdoors, the constituent components are deteriorated by ultraviolet rays, causing defects such as chalking or swelling or peeling of the coating film.

In this regard, a method is known in which a coating film having good water resistance and weather resistance is further laminated on the coating film of the fire-resistant paint as an overcoating material. Even with this method, it is difficult to maintain the inherent fire resistance of the fire-resistant coating film for a long period of time because of insufficient adhesion to the material.

[0009]

Therefore, the main object of the present invention is to obtain a composite refractory coating layer having excellent long-term weather resistance.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in view of the above problems, and as a result, found that a coating film formed from a fire-resistant coating material having a specific composition has a certain adhesiveness with an overcoat material. As a result, it has been found that a coating film having excellent long-term weather resistance can be provided, and the present invention has been completed.

That is, the present invention relates to the following composite fireproof coating composition, composite fireproof coating layer and method for forming the same.

1. At least one decomposition type foaming agent containing vinyl-based thermoplastic synthetic resin, petroleum resin, phosphorus-based flame retardant, melamine-based compound, triazine-based compound, N-nitroso compound, azo compound, sulfone hydrazide compound and their derivatives, and A composition for forming a composite fireproof coating layer, which comprises a polyhydric alcohol-based carbonized layer-forming agent and a chlorine-based plasticizer.

2. A method for forming a composite fireproof coating layer, which comprises forming a fireproof coating layer comprising the composition as described in 1 above on an object to be coated, and further applying an overcoat material on the fireproof coating layer.

3. 4. The forming method according to 3 above, wherein the topcoat material is a silicone-modified acrylic resin or fluorourethane resin as a main component.

4. A composite fireproof coating layer formed by the forming method as described in 2 or 3 above.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail along with its embodiments.

The vinyl-based thermoplastic synthetic resin serves as a base for mainly dispersing other compounding components of the composite fire-resistant coating layer forming composition, and is used for maintaining the composite fire-resistant coating layer forming composition in a layered form. It becomes the main material for film formation.

The vinyl-based thermoplastic synthetic resin is not particularly limited as long as it has the above-mentioned functions, and examples thereof include polyvinyl chloride, polyethylene, ethylene-vinyl acetate synthetic resin, vinyl acetate-veova synthetic resin, vinyltoluene butadiene and vinyltoluene. Acrylate, vinyltoluene methacrylate, etc. are mentioned, and these can be used individually or in combination of 2 or more types.

Of these, vinyltoluene-based compounds such as vinyltoluene butadiene, vinyltoluene acrylate and vinyltoluene methacrylate are preferable, and vinyltoluene butadiene and vinyltoluene acrylate are more preferable.

The molecular weight of the vinyl-based thermoplastic synthetic resin is not particularly limited, but usually the weight average molecular weight is from 50,000 to 50,000.
It may be about 200,000.

As the petroleum resin, known ones can be used as they are, and commercially available ones can also be used. Examples of the type of petroleum resin include, for example, aliphatic (C ₅ type) petroleum derived from a C ₅ fraction as a raw material in a cracked fraction produced as a by-product from an ethylene plant that produces ethylene, propylene and the like by steam cracking of petroleum Resin, aromatic (C ₉ series) petroleum resin using C ₉ fraction as a raw material, aliphatic / aromatic copolymerization (C ₅ C ₉ series) petroleum resin using both as raw materials, and high-purity dicyclopentadiene Examples thereof include alicyclic (DCPD) petroleum resins and the like. These petroleum resins may be used alone or in combination of two or more kinds. Among these petroleum resins, it is desirable to use an alicyclic (DCPD) petroleum resin because of its excellent weather resistance and good adhesiveness with the overcoat material.

By blending a petroleum resin, particularly when a topcoat material having excellent weather resistance is formed on the surface of the fireproof coating layer formed from the composition for forming a composite fireproof coating layer, excellent adhesion and weather resistance are obtained. Exerts sex.

The blending amount (solid content) of the petroleum resin may be appropriately changed depending on the type of the vinyl-based thermoplastic synthetic resin used, the type of the petroleum resin used, the site where the coating film is used, etc.
Usually, about 10 to 60 parts by weight, preferably 15 to about 10 parts by weight, based on 100 parts by weight of the solid content of the vinyl-based thermoplastic synthetic resin.
45 parts by weight. If the amount is less than 10 parts by weight, the adhesion to the overcoat material having excellent weather resistance may be insufficient,
If it exceeds 60 parts by weight, the foamed carbonized heat insulating layer may be burned.

The phosphorus-based flame retardant mainly suppresses or prevents the combustion of the foamed carbonized heat insulating layer by the flame retardant action, and the type thereof is not particularly limited as long as it has this action. For example, tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, tri (β-chloroethyl) phosphate, tributyl phosphate, tri (dichloropropyl) phosphate, triphenyl phosphate, tri (dibromopropyl) phosphate, chlorophosphonate, bromophosphonate , Diethyl-N, N-bis (2-hydroxyethyl) aminomethyl phosphate, organic phosphorus compounds such as di (polyoxyethylene) hydroxymethylphosphonate, chlorides such as phosphorus trichloride and phosphorus pentachloride, ammonium phosphate, Examples thereof include phosphoric acid compounds such as ammonium polyphosphate. These flame retardants may be used alone or in combination of two or more. Among these, particularly, ammonium polyphosphate is used because it has excellent flame retardancy because it has both a dehydration cooling action and a nonflammable gas generating action, and has the advantage that the compounding amount of the foaming agent described below can be reduced. Is preferred.

The amount of the phosphorus-based flame retardant compounded may be appropriately set depending on the type of the flame retardant agent, etc., but is usually 20 per 100 parts by weight of the solid content of the vinyl-based thermoplastic synthetic resin.
The amount may be about 0 to 600 parts by weight, preferably 300 to 500 parts by weight. If the amount is less than 200 parts by weight, the foaming ratio becomes low and the fire resistance may not be exhibited.
If the amount is more than 600 parts by weight, the strength of the foamed carbonized heat insulating layer becomes low and the steel frame cannot be sufficiently protected. The foaming agent is
It decomposes with an increase in temperature to generate an incombustible gas, and forms a polyhydric alcohol carbide, which will be described later, in a foamed porous form. As these foaming agents, known ones can be used as they are as long as they have such a foaming action,
For example, melamine-based compounds such as melamine, triazine-based compounds such as trihydrazinotriazine, dinitrosopentamethylenetetramine, N-nitroso compounds such as N, N-dinitroso-N, N-dimethylterephthalamide, azobisisobutyronitrile. , Azo compounds such as azodicarbonamide, benzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide, sulfone hydrazide compounds such as p, p-oxy-bis (benzenesulfonyl hydrazide), and derivatives thereof. These may be used alone or in combination of two or more. Among these, melamine, trihydrazinotriazine and the like are preferable in view of the foaming initiation temperature, handling, availability and the like.

The blending amount of the foaming agent may be determined depending on the type of the foaming agent to be used, the site where the coating film is used, etc., but is usually 40 with respect to 100 parts by weight of the solid content of the above vinyl-based thermoplastic synthetic resin. ~ 120 parts by weight, preferably 60-9
It may be 0 parts by weight. If it is less than 40 parts by weight, voids may occur in the foamed carbonized heat insulating layer. Also, 120
If the amount is more than parts by weight, the expansion ratio will be low.

The polyhydric alcohol-based carbonized layer forming agent carbonizes mainly with an increase in temperature to form a foamed porous material of a carbide by the effect of the above-mentioned foaming agent. The polyhydric alcohol-based carbonized layer-forming agent is not particularly limited as long as it has the above-mentioned action, and examples thereof include starch, casein, pentaerythritol, dipentaerythritol, and trimethylpropane. Among these, dipentaerythritol and the like are preferable. One or two or more of these polyhydric alcohol-based carbonized layer forming agents may be used.

The blending amount of the polyhydric alcohol-based carbonized layer forming agent can be appropriately changed depending on the site where the coating film is used, etc., but usually, the solid content of the vinyl-based thermoplastic synthetic resin is 1%.
The amount may be about 40 to 120 parts by weight, preferably 60 to 90 parts by weight, based on 00 parts by weight.

The chlorine-based plasticizer is added in order to improve the toughness of the formed composite fireproof coating layer, and the type thereof is not particularly limited as long as it has such properties. For example, chlorinated paraffin-based, chlorinated polyolefin-based, chlorinated aliphatic ester and other chlorine-based plasticizers can be used. These chlorine-based plasticizers are
You may use together or 2 types or more. Among these chlorine plasticizers, it is preferable to use chlorinated paraffin.

The blending amount of the chlorine-based plasticizer may be appropriately set depending on the site to be used and the like, but usually 50 to 1 per 100 parts by weight of the solid content of the vinyl-based thermoplastic synthetic resin.
It may be about 70 parts by weight, preferably 70 to 130 parts by weight. If it is less than 50 parts by weight, foaming will be insufficient, and if it exceeds 170 parts by weight, the coating film tends to be too soft.

In addition to these components, the composition of the present invention may contain titanium dioxide, talc, calcium carbonate, sodium carbonate, zinc oxide, clay, clay, shirasu, if necessary, as long as the effect of the present invention is not reduced. Mica, fiberglass,
Glass flakes, silica sand, fillers such as cold water stone, benzene,
Solvents (diluting solvents) such as toluene, xylene, mineral spirits, methyl ethyl ketone, methyl isobutyl ketone, drying regulators such as ethylene glycol, organic bentonite, amide wax, viscosity regulators such as castor oil,
Various additives such as antifoaming agents such as silicone oil can also be blended.

The composition of the present invention is not particularly limited in the mixing order as long as the above-mentioned respective components can be mixed uniformly. In particular, a vinyl type thermoplastic synthetic resin is mixed with a decomposing type foaming agent and a polyhydric alcohol type carbon layer forming agent. After that, it is desirable to mix the petroleum resin and the diluting solvent, and then mix the chlorine-based plasticizer.

Specifically, for example, a thermoplastic vinyl synthetic resin is put into a mixing and stirring tank, and a decomposing type foaming agent and a polyhydric alcohol type carbonized layer forming agent are blended uniformly while mixing and stirring by a dissolver or the like. After the dispersion, the petroleum resin and the solvent for dilution are mixed, and then the chlorine-based plasticizer is mixed. With such a method, the fluidity of the petroleum resin can be effectively utilized to reduce the amount of the solvent blended.

The composite refractory coating layer of the present invention is a topcoat material having excellent long-term weatherability on the surface of a fire-resistant coating layer formed from the above composition for forming a composite refractory coating layer on an object to be coated such as a steel frame. It is formed by applying.

The refractory coating layer can be obtained by applying the composition by a known coating method such as brush coating, spraying or roller coating, and drying. The film thickness of the coating film may be appropriately determined according to the site to be used, the type and shape of the article to be coated, etc., but is usually about 0.3 to 3 mm. However, the composition of the present invention can be applied in a thickness of 3 mm or more depending on the composition.

The article to be coated is not particularly limited,
It can be applied to virtually any material such as metal materials such as iron, stainless steel and aluminum, materials obtained by metal plating such as zinc plating, inorganic hardened materials such as concrete and mortar, and other plastics and wood.

As a top coat material having excellent long-term weather resistance, JIS
A 6909-1995 “Construction finish coating material” 6.20 Weather resistance test It is not particularly limited as long as it has the performance of one to three weather resistance types in the B method. For example, a silicone-modified acrylic resin,
A resin mainly containing a fluorine-containing urethane resin is preferable because the coating film is less likely to be contaminated.

[0038]

Since the composition of the present invention is composed of a specific composition containing a petroleum resin, the fire-resistant coating layer has excellent adhesion to the top coating material and is used as a fire-resistant coating material having fire resistance, heat insulation and the like. The original function of can be maintained for a long period of time.

Further, the above fire-resistant coating layer is unlikely to be cracked due to drying shrinkage, and can be formed as a thick film of several mm.

Furthermore, the composition of the present invention is excellent in thixotropic properties, the coating film does not sag even when it is thickly sprayed, and it can be applied thickly to virtually every site. Also,
Even when the pump is pumped, it shows a viscosity that makes it easy to pump, and it has excellent handleability and workability.

The composition of the present invention having such characteristics is useful in the field of fireproof coatings for preventing the strength of structures from decreasing due to temperature rise when a fire occurs, mainly in civil engineering and building structures.

[0042]

EXAMPLES Examples and comparative examples are shown below to further clarify the features of the present invention. The test method in this example is as follows.

Fire resistance performance test JIS K 1304 “Fire resistance test method for building structures”, “4.
Based on the standard heating curve specified in "Heating grade; Appendix", the one side of the test piece was heated in an electric furnace and the backside temperature of the hot-rolled steel sheet reached 600 ° C. ) Evaluated. Further, the test piece was evaluated for the foaming ratio of the dried coating film and the state (appearance) of the foamed layer.

Coating film physical property test Each test piece is referred to in JIS K 5400 “General paint test method”, “9.8
After the accelerated test for 350 hours with a sunshine carbon arc lamp type weather resistance tester specified in "accelerated weather resistance test", the state of the coating film on the surface of the test piece was evaluated by visual observation.

Subsequently, the test piece after the test was subjected to a 10-cycle test based on JIS K 5400 "General paint test method", "9.4" Wet resistance repeatability "". The contents of one cycle were 18 hours in 20 ° C. clear water, 3 hours at 20 ° C. in the atmosphere, and 3 hours at 50 ° C. in the atmosphere. After conducting the test in this manner, the state of the coating film on the surface of the test piece was evaluated by visual observation. The evaluation method for these tests is "Evaluation Criteria for Paint Films (1970)" published by Japan Paint Inspection Association.
The evaluation was performed based on the "blister evaluation" and "my evaluation".

Comprehensive Evaluation: A composite fireproof coating layer having excellent long-term weather resistance can be used, and an unusable composite fireproof coating layer is shown as X.

Example 1 A vinyltoluene acrylate resin solution as a vinyl-based thermoplastic resin was added to a mixing and stirring tank at 100 in terms of solid content.
80 parts by weight of melamine as a foaming agent, 85 parts by weight of dipentaerythritol as a carbonized layer forming agent, and 120 parts by weight of titanium dioxide as a filler were added thereto and uniformly dispersed. . Furthermore, 40 parts by weight of an alicyclic hydrocarbon-based petroleum resin and 300 parts by weight of a solvent for dilution (xylene) were added and sufficiently mixed until uniform, then 400 parts by weight of ammonium polyphosphate was added, and a plasticizer was further added. As chlorinated paraffin 9
0 parts by weight was added and mixed to obtain a composite fireproof coating composition.
The raw materials used and their formulations are also shown in Tables 1 and 2.

The above composition was added to 300 mm × 300 mm × 9 mm
(A) and 150 mm × 300 mm × 2.3 mm (B) hot-rolled steel sheets were used as base materials and spray-coated with a coating amount of 3.0 kg / m ² , respectively, and dried and cured for 5 days. Further, a silicon-modified acrylic resin-based paint (“Elastic Lyricatite Enamel”, manufactured by SK Kaken Co., Ltd.) was applied as a top coat material at a coating amount of 0.12 kg / m ² and dried and cured for 1 week.

The obtained test piece A was subjected to a fire resistance performance test, and the test piece B was subjected to a coating film physical property test. The results are shown in Table 4.

As a result of the above, since the coating layer obtained above has excellent adhesion to the overcoat material, it does not cause blistering or cracking, and there is no abnormality in the state of the foamed carbonized heat insulating layer in terms of fire resistance. The expansion ratio was also high, and the fireproof time was 65 minutes, which showed excellent performance.

Examples 2 to 3 Except that the raw materials shown in Table 1 were used and the formulations shown in Table 2 were used,
A composite fireproof coating layer forming composition was produced in the same manner as in Example 1, a coating layer was formed, and each test was conducted. The results are shown in Table 4. As shown in Table 4, the obtained coating layer was excellent in long-term weather resistance as in Example 1 and showed excellent fire resistance.

Examples 4 to 6 Except that the raw materials shown in Table 1 were used and the formulations shown in Table 2 were used,
A composition for forming a composite refractory coating layer was produced in the same manner as in Example 1.

Then, a coating was carried out in the same manner as in Example 1 except that a fluorourethane resin-based paint (“elastic fussolone” manufactured by SK Kaken Co., Ltd.) was used as the top coat material (coating amount 0.12 kg / m ² ). Layers were obtained.

The same tests as in Example 1 were carried out on the obtained coating layer. The results are shown in Table 4. As shown in Table 4, the obtained coating layer was excellent in long-term weather resistance as in Example 1 and showed excellent fire resistance.

Comparative Example 1 The raw materials shown in Table 1 were used, except that the formulation shown in Table 3 was used.
A composition was produced in the same manner as in Example 1, a coating layer was formed, and each test was performed. The results are shown in Table 5. As shown in Table 5, since the obtained coating layer contains no petroleum resin, the swelling degree of the coating film in the coating film physical property test is 4 mm or more (average diameter), and the total area of the blister is Was 8% or less of 0.5% of the whole, and it was found that the long-term weather resistance was insufficient.

COMPARATIVE EXAMPLE 2 Except that the raw materials shown in Table 1 were used and the formulations shown in Table 3 were used,
A composition was produced in the same manner as in Example 1, a coating layer was formed, and each test was performed. The results are shown in Table 5. As shown in Table 5, there was no problem in the coating film physical property test, but since only non-vinyl type styrene-methacrylic acid alkyl ester-acrylic acid alkyl ester copolymer resin was used, the foamed carbonized layer It was found that the fire resistance was inferior due to falling off.

COMPARATIVE EXAMPLE 3 The raw materials shown in Table 1 were used, except that the composition shown in Table 3 was used.
A composition was produced in the same manner as in Example 1, a coating layer was formed, and each test was performed. The results are shown in Table 5. As shown in Table 5, since only the petroleum resin was used alone without using the vinyl-based thermoplastic resin, the swell size of the coating film was 4 mm or more (average diameter) in the coating film physical property test. The area was 11 to 30% of the whole, which was evaluated as 2-VL, and it was found that the long-term weather resistance was insufficient. Further, combustion ash of the foamed carbonized layer was recognized, and the fire resistance was insufficient.

Comparative Example 4 Except that the raw materials shown in Table 1 were used and the formulations shown in Table 3 were used,
A composition was produced in the same manner as in Example 1, a coating layer was formed, and each test was performed. The results are shown in Table 5. As shown in Table 5, since the petroleum resin is not blended, the swelling degree of the coating film is 4 mm or more (average diameter) in the coating film physical property test, and the total area of blisters is 0.5% of the whole. The following evaluation was 8-VL, and it was found that the long-term weather resistance was insufficient. Further, the fire resistance time was decreased, the expansion ratio of the expanded carbonized layer was decreased, and the fire resistance performance was also insufficient.

COMPARATIVE EXAMPLE 5 Except that the raw materials shown in Table 1 were used and the formulation shown in Table 3 was used.
A composition was produced in the same manner as in Example 1, a coating layer was formed, and each test was performed. The results are shown in Table 5. As shown in Table 5, there was no particular problem in the coating film physical property test, but since the non-vinyl type styrene-alkyl methacrylate ester-alkyl acrylate copolymer resin was used in combination with the petroleum resin, It was found that the fire resistance was inferior due to falling off.

COMPARATIVE EXAMPLE 6 Except that the raw materials shown in Table 1 were used and the formulations shown in Table 3 were used,
A composition was produced in the same manner as in Example 1, a coating layer was formed, and each test was performed. The results are shown in Table 5. As shown in Table 5, since the blending amount of the petroleum resin is small, the blister size of the coating film is 0.2 to 0.5 mm in the coating film physical property test.
Above (average diameter), the total area of swelling is 0.5 of the total
The evaluation was 8-S, which was less than%, and it was found that the long-term weather resistance was insufficient.

COMPARATIVE EXAMPLE 7 Except that the raw materials shown in Table 1 were used and the formulations shown in Table 3 were used,
A composition was produced in the same manner as in Example 1, a coating layer was formed, and each test was performed. The results are shown in Table 5. As shown in Table 5, it was found that since the amount of the petroleum resin blended was large, the foamed carbonized layer fell off and the fire resistance performance was inferior.

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

[Table 3]

[0065]

[Table 4]

[0066]

[Table 5]

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Hideo Motoki 1-25-10 Shimizu, Ibaraki-shi, Osaka SK Research Institute, Inc. (72) Inventor Tomio Ouchi 2-chome, Hibita, Chofu-shi, Tokyo 19 No. 1 in Kashima Construction Co., Ltd. Technical Research Institute (72) Inventor Keiichi Miyamoto No. 19-1 Tobita-ryu, Chofu City, Tokyo Kashima Construction Co., Ltd. Technical Research Institute

Claims (12)

[Claims] 1. A decomposable foaming agent comprising a vinyl-based thermoplastic synthetic resin, a petroleum resin, a phosphorus-based flame retardant, a melamine-based compound, a triazine-based compound, an N-nitroso compound, an azo compound, a sulfone hydrazide compound and their derivatives. A composition for forming a composite refractory coating layer, comprising at least one kind of polyhydric alcohol type carbonized layer forming agent and chlorine type plasticizer. 2. A thermoplastic vinyl synthetic resin (solid content) 1
10 to 60 parts by weight of petroleum resin to 00 parts by weight,
Phosphorus flame retardant 200 to 600 parts by weight, melamine compound, triazine compound, N-nitroso compound, azo compound, sulfone hydrazide compound and at least one decomposable foaming agent consisting of a derivative thereof 40 to 120 parts by weight, The composition for forming a composite fireproof coating layer according to claim 1, which contains 40 to 120 parts by weight of a polyhydric alcohol type carbonized layer forming agent and 50 to 170 parts by weight of a chlorine type plasticizer. 3. The composition according to claim 1, wherein the vinyl-based thermoplastic synthetic resin is a vinyltoluene-based synthetic resin. 4. A composite comprising a refractory coating layer comprising the composition according to any one of claims 1 to 3 formed on an article to be coated, and a top coating material further applied onto the refractory coating layer. Method for forming fireproof coating layer. 5. The top coat material is mainly composed of silicone-modified acrylic resin or fluorourethane resin.
The forming method as described above. 6. A composite refractory coating layer formed by the method according to claim 4 or 5. 7. A composition for forming a composite refractory coating layer, which comprises a vinyltoluene synthetic resin, an alicyclic hydrocarbon petroleum resin, ammonium polyphosphate, melamine, dipentaerythritol and chlorinated paraffin. 8. A vinyltoluene synthetic resin (solid content) 10
Aliphatic hydrocarbon-based petroleum resin (solid content) 10 to 60 parts by weight, ammonium polyphosphate 200 to 0 parts by weight
The composition for forming a composite refractory coating layer according to claim 6, which comprises ˜600 parts by weight, melamine 40 to 120 parts by weight, dipentaerythritol 40 to 120 parts by weight, and chlorinated paraffin 50 to 170 parts by weight. 9. A composite fireproof coating layer comprising a fireproof coating layer comprising the composition according to claim 7 or 8 formed on an article to be coated, and a topcoat material further applied onto the fireproof coating layer. Forming method. 10. The method according to claim 9, wherein the topcoat material is a silicone-modified acrylic resin or fluorourethane resin as a main component. 11. A composite refractory coating layer formed by the method according to claim 9 or 10. 12. A vinyl type thermoplastic synthetic resin is mixed with a decomposing type foaming agent and a polyhydric alcohol type carbonized layer forming agent, then a petroleum resin and a diluting solvent are mixed, and then a phosphorus type flame retardant is mixed. A method for producing a composition for forming a composite fireproof coating layer, which comprises mixing a chlorine-based plasticizer.